EP0445538B1 - Wear resistant titanium nitride coating and methods of application - Google Patents

Wear resistant titanium nitride coating and methods of application Download PDF

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Publication number
EP0445538B1
EP0445538B1 EP91101621A EP91101621A EP0445538B1 EP 0445538 B1 EP0445538 B1 EP 0445538B1 EP 91101621 A EP91101621 A EP 91101621A EP 91101621 A EP91101621 A EP 91101621A EP 0445538 B1 EP0445538 B1 EP 0445538B1
Authority
EP
European Patent Office
Prior art keywords
substrate
wire
coating
nitrogen
titanium nitride
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP91101621A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP0445538A1 (en
Inventor
Zbigniew Zurecki
Edward Andrew Hayduk, Jr.
John Gregory North
Robert Bruce Swan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Air Products and Chemicals Inc
Original Assignee
Air Products and Chemicals Inc
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Air Products and Chemicals Inc filed Critical Air Products and Chemicals Inc
Publication of EP0445538A1 publication Critical patent/EP0445538A1/en
Application granted granted Critical
Publication of EP0445538B1 publication Critical patent/EP0445538B1/en
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/131—Wire arc spraying
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T50/00—Aeronautics or air transport
    • Y02T50/60—Efficient propulsion technologies, e.g. for aircraft

Definitions

  • the present invention pertains to industrial articles such as screens for cominution devices which are normally subject to mechanical wear during use and methods for extending the service life of such parts.
  • a number of methods are available for surface hardening or depositing corrosion and wear resistant materials on industrial parts.
  • the oldest known methods are diffusion treatments, nitriding and carburizing of ferrous based materials.
  • the disadvantage in using these techniques is that they involve subjecting the parts to elevated temperatures. Apart from the high costs associated with the energy and operation time, subjecting a part to elevated temperatures can cause size changes and loss of mechanical properties which would render the part unsuitable for use and/or would require a further heat treating operation and a subsequent cleaning operation to be performed after the surface treatment.
  • Electroplating most commonly used to produce hard chromium or nickel coatings, involves cleaning the parts to be coated to a high degree and involves toxic solutions which are costly when disposed of in an environmentally safe manner.
  • Plasma spraying especially if performed in a vacuum or atmosphere chamber, will yield dense homogeneous coatings but is expensive and therefore limited in use.
  • High velocity detonation guns can deposit dense ceramic coatings on substrates but the equipment, feed powders and processing are very expensive.
  • JP-A-60 092 461 makes use of a Ti powder to produce a coating on the substrate. This powder is reacted with for example nitrogen gas by plasma art discharge and molten by use of high-output laser. After all the resulting coating is cooled with water.
  • Electric arc spraying with inert gases can produce dense, homogeneous coatings which bond well to a variety of substrate materials.
  • Arc-sprayed titanium nitride which does not require high enthalpy flame is a cold process compared to the high heat input plasma and flame spray processes which can damage or distort the substrate material.
  • the capital equipment and operating costs are less than one-half that of the plasma high velocity spraying methods and about order of magnitude less than that of the chemical vapor deposition.
  • the surface to be coated requires no special preparation other than grit blasting.
  • a titanium nitride coating can be applied by exposing a substrate to an effluent from an electric arc thermal spray gun operated in the atmosphere with a current supply of between 100 and 400 A and a potential difference ot between 28 and 48 V, using a pretreated titanium wire, said wire being pretreated by annealing in nitrogen to increase the nitrogen content of the wire to at least 500 ppm, and a nitrogen gas as the atomizing/propelling gas being fed to the nozzle as a gas stream at between 206.6 and 894.4 kPa (30 and 130 psia) whereby a substatially titanium nitride coating having a thickness of at least 0.0254 mm (0.001 inch) is produced on said substrate.
  • One embodiement of the invention includes coatings nitrogen arc sprayed using two different wire materials where at least one of them is said nitrogen pretreated titanium wire.
  • Figure 1 is a schematic representation of a typical electric arc spray system employed to make the articles and practice the process of the present invention.
  • Figure 2 is a photomicrograph of the structure of titanium wire before treatment.
  • Figure 3 is a photomicrograph of the structure of titanium wire after pre-nitriding.
  • One method of enhancing the wear resistance of industrial parts would be to deposit a titanium nitride coating on the surfaces of the parts that are subject to wear. It has been discovered that if the electric arc spray process is used to apply such coatings and high purity nitrogen is substituted for air as a propelling gas the titanium wire is melted and the titanium is nitrided with minimum oxidation between the arc spraying device and the substrate to deposit a titanium nitride coating.
  • the arc spray process can be used without an atmosphere chamber or a furnace or subsequent nitriding of the coating. A particularly effective coating is achieved if the titanium wire is nitrided prior to being used in the electric arc spray device.
  • the nitrogen used as the propelling (atomizing) gas during the electric arc thermal spray process reacts with the titantium feed wire to produce the titanium nitrogen compound in flight.
  • the molten droplets land on the surface of the article being coated they solidify thus forming a hard titanium nitride base coating that protects against wear and corrosion.
  • Electric arc spraying of a titanium coating utilizing nitrogen as a propelling gas is inexpensive as compared to deposition by plasma, high velocity combustion spraying, chemical vapor deposition and physical vapor deposition techniques.
  • titanium nitride and titanium oxide are non-toxic as compared to chromium and nickel-phosphorous used in other hard facing techiques, thus the coating is suitable for use in food processing equipment.
  • arc spraying takes minutes rather than hours that may be required for other processes, leaves no toxic byproducts and requires a minimal capital investment.
  • the arc spray system 10 includes an arc gun 12, a constant voltage power source 14, a control console 16 and a wire feed device represented by wire spools 18 and 20 respectively.
  • the arc spray gun 12 includes two sets of feed rollers 22, 24 to move separate wires 26, 28 respectively, through the gun to the nozzle end 30 where due to electrical current of different polarities (e.g., as shown in the drawing) an arc is struck between the wires 26 and 28.
  • compressed nitrogen gas is introduced into the arc on 12 as shown by the arrow 32.
  • the nitrogen gas exists the nozzle 30, where it causes the molten metal to be broken up into a stream of droplets.
  • the compressed gas in addition to atomizing the metal, propels the atomized metal (spray stream) toward a substrate 34 such as a conventional Hammermill screen 34.
  • a substrate 34 such as a conventional Hammermill screen 34.
  • reaction with nitrogen forms a titanium nitride compound.
  • the substrate 34 can be mounted vertically or horizontally and either it or the arc gun 12 can be oscillated to provide a uniform coating over the length of the electrode.
  • Wire feeders 18 and 20 can also include a pair of rollers 36, 38 to help feed the wire from the spools to the gun 12.
  • the feed rolls in the gun and the wire feeds can either push, pull or use a combination of both techniques to move the wire through the arc gun 12.
  • the titanium wire pre-treatment was developed when it was realized that N2-sprayed Ti x N coatings were both nitrogen (N) deficient and prone to in-flight oxidation.
  • N nitrogen
  • the different microhardness (e.g., 269 vs. 150 VHN) on the cross-section of the N2 annealed and initially 'hard' and 'soft' Ti-wires indicates that N2 annealing can be at temperatures higher than 1000°C.
  • TABLE 2 shows the 8-fold [N] pickup in the Ti-wire resulting from our 1000°C N2 annealing.
  • Ti x N coatings were deposited using the N2 annealed wires and compared to the coatings produced previously using the as-supplied wires and/or the N2 post-deposition annealing.
  • the appearance, surface roughness, self-bonding ability, and adhesion to the substrate (bend test) of the new coatings were the same as in the case of the coatings deposited in the past.
  • the Knoop microhardness measurements revealed significant differences between the coatings.
  • the coating deposited using the N2 annealed wire was as hard as the coating which was applied by depositing essentially pure titanium followed by a post-deposition anneal in N2 atmosphere.
  • Both these coatings were much harder than the 'basic' coating produced with the as-supplied wire with no post-deposition annealing.
  • the N2 wire pretreatment was found to improve hardness of the Ti x N coating by increasing the nitrogen content and improving the nitride stoichiometry (lower x). Nevertheless, the increased nitrogen content did not reduce the self-bonding ability of the Ti x N deposits.
  • Microhardness of the new coating is at least equivalent to that of the post-deposition annealed coatings, which makes the annealing of the coated parts unnecessary.
  • both the pretreatment and post-deposition annealing steps can be used as two independent tools for the coating hardness control. It was also observed that the wire pretreatment improved the arc stability by lowering the wire friction in the gun conduits.
  • any technically pure, i.e. unalloyed, titanium wire with no special requirements or specs on purity levels, e.g. no spec. on Fe, V, etc. can be used.
  • a technically pure titanium wire should have no more than 100 ppm of nitrogen (on wt. basis). Any titanium physical condition, e.g. soft, hard, or half-hard is acceptable.
  • Figure 2 is a photomicrograph of the structure of a typical wire before treatment.
  • the microstructure of the pre-nitrided (annealed) wire should show coarse circular grain growth from the surface toward the core of the wire with corresponding degrees of hardness (VHN) from the surface to the core.
  • a uniform wear and corrosion resistant coating consisting primarily of titanium nitride can be deposited on a variety of substrate materials.
  • the coating is deposited by electric arc spray using 15.7 or 7.6 mm (0.062 or 0.030 inch) diameter titanium wire that has been pretreated as set out above and nitrogen as the propelling (atomizing) gas. Nitrogen is substituted for high purity air as the propelling gas so that the titanium is further nitrided and oxidation is minimized.
  • Two spools of titanium wire are feed at a constant rate into the gun 12 where they arc across at a potential difference of between 28 and 48 V and 100-400 A.
  • one spool of the wire may feed the spraying gun with another coating material which will form with the Ti x N alloyed for pseudo-alloyed coatings.
  • This other material may include hard Fe, Cr, Ni, Mo, and W alloys and compounds as well as soft bonding non-ferrous metals and alloys.
  • the coatings produced by the simultaneous use of the Ti and non-Ti wires offer lower hardness but higher impact resistance. The required spraying conditions remain unchanged.
  • the nitrogen gas stream is feed to the nozzle at between 206.6 and 894.9 kPa (30 and 130 psig). The molten droplets react in flight with the nitrogen gas and form the titanium nitride coating on the substrate 34.
  • the stand-off distance between the gun and a substrate is between 7.6 and 20.3 cm (3 and 8 inches).
  • the substrate is grit blasted before spraying in order to increase the strength of the mechanical bond between the coating and the substrate.
  • the coating itself can be deposited to a thickness ranging from 0.025 mm (0.001 inches) to several mm (inches) in depth.
  • Coated parts have shown increased wear and corrosion resistance. Specifically, screens from Hammermills use to cryogenically grind rubber were coated under the above condition with three passes used to deposit a coating having a nominal thickness of 0.03 cm 0.012 inches. Screens coated according to the invention have shown service lives between 2 and 10 times as long as uncoated screens. Corrosion exposure tests were performed by placing coated parts in seawater for extended periods of time with no apparent effect on the coating.
  • the titanium-nitrogen compound forming the coating which provides increased wear and corrosion-resistance over that of the metallic substrate can show a coating hardness in the range of between 860 to 1500 (VHN) micro hardness as measured by the Vickers method. This is harder by a factor of between 5 and 11 than the normal substrate materials.
  • the process of the present invention can be applied to any material that will accept a titanium nitride bonded coating.
  • the coatings will be effective to increase the wear resistance and can be placed on the substrate by an economical method.
  • the process of the present invention was applied to an air-jet pulverizer which is used to grind metal salt material. Previous attempts by the user to grind a metal salt material have resulted in graying of the light material due to erosion of the interior surfaces of the mill. Coating a laboratory mill resulted in grinding of the salt material with no apparent contamination since there was no graying of the white material produced.
  • Wear clips from a centrifugal kelp processing machine were coated according to the present invention and were found to last twice as long as parts which the user had coated with tungsten carbide.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Physics & Mathematics (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Coating By Spraying Or Casting (AREA)
  • Solid-Phase Diffusion Into Metallic Material Surfaces (AREA)
  • Physical Vapour Deposition (AREA)
EP91101621A 1990-02-06 1991-02-06 Wear resistant titanium nitride coating and methods of application Expired - Lifetime EP0445538B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US07/477,400 US5066513A (en) 1990-02-06 1990-02-06 Method of producing titanium nitride coatings by electric arc thermal spray
US477400 1990-02-06

Publications (2)

Publication Number Publication Date
EP0445538A1 EP0445538A1 (en) 1991-09-11
EP0445538B1 true EP0445538B1 (en) 1995-04-19

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ID=23895765

Family Applications (1)

Application Number Title Priority Date Filing Date
EP91101621A Expired - Lifetime EP0445538B1 (en) 1990-02-06 1991-02-06 Wear resistant titanium nitride coating and methods of application

Country Status (11)

Country Link
US (1) US5066513A (xx)
EP (1) EP0445538B1 (xx)
JP (1) JP2567304B2 (xx)
KR (1) KR930007147B1 (xx)
CN (1) CN1019642B (xx)
BR (1) BR9100458A (xx)
CA (1) CA2034981A1 (xx)
DE (1) DE69108963T2 (xx)
ES (1) ES2073598T3 (xx)
MX (1) MX170472B (xx)
ZA (1) ZA91888B (xx)

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US5254359A (en) * 1989-06-02 1993-10-19 Air Products And Chemicals, Inc. Method of forming titanium nitride coatings on carbon/graphite substrates by electric arc thermal spray process using titanium feed wire and nitrogen as the atomizing gas
US5314601A (en) * 1989-06-30 1994-05-24 Eltech Systems Corporation Electrodes of improved service life
US5213848A (en) * 1990-02-06 1993-05-25 Air Products And Chemicals, Inc. Method of producing titanium nitride coatings by electric arc thermal spray
JPH0414784A (ja) * 1990-05-08 1992-01-20 Masao Iwanaga 放電素子、その製造方法および応用装置
US5264376A (en) * 1991-06-24 1993-11-23 Texas Instruments Incorporated Method of making a thin film solar cell
US5485333A (en) * 1993-04-23 1996-01-16 Eastman Kodak Company Shorted DMR reproduce head
AT400248B (de) * 1993-08-19 1995-11-27 Haller Rudolf Ing Schneideplatten-paar für elektrische haarschneidemaschinen
US5879817A (en) * 1994-02-15 1999-03-09 Eltech Systems Corporation Reinforced concrete structure
US5441235A (en) * 1994-05-20 1995-08-15 Eaton Corporation Titanium nitride coated valve and method for making
US6060162A (en) * 1995-06-08 2000-05-09 Phelps Dodge Industries, Inc. Pulsed voltage surge resistant magnet wire
WO1996042089A1 (en) 1995-06-08 1996-12-27 Weijun Yin Pulsed voltage surge resistant magnet wire
WO1997049497A1 (en) * 1996-06-24 1997-12-31 Tafa, Incorporated Apparatus for rotary spraying a metallic coating
WO1998000574A1 (en) * 1996-06-28 1998-01-08 Metalplus (Proprietary) Limited Thermal spraying method and apparatus
GB2320929B (en) * 1997-01-02 2001-06-06 Gen Electric Electric arc spray process for applying a heat transfer enhancement metallic coating
US6003788A (en) * 1998-05-14 1999-12-21 Tafa Incorporated Thermal spray gun with improved thermal efficiency and nozzle/barrel wear resistance
KR100370564B1 (ko) * 1998-12-14 2003-03-31 주식회사 포스코 혼합용사합금분말의폭발용사코팅방법
US6319604B1 (en) 1999-07-08 2001-11-20 Phelps Dodge Industries, Inc. Abrasion resistant coated wire
DE10111109A1 (de) * 2001-03-08 2002-10-31 Deutsche Titan Gmbh Verfahren zum Herstellen einer Titanfolie mit nitrierter Oberflächenbeschichtung
US6914093B2 (en) 2001-10-16 2005-07-05 Phelps Dodge Industries, Inc. Polyamideimide composition
DE10345827A1 (de) * 2003-10-02 2005-05-04 Daimler Chrysler Ag Verfahren zur Beschichtung von metallischen Substraten mit oxidierenden Werkstoffen mittels Lichtbogendrahtspritzen
US7973122B2 (en) * 2004-06-17 2011-07-05 General Cable Technologies Corporation Polyamideimide compositions having multifunctional core structures
US20080193637A1 (en) * 2006-01-03 2008-08-14 Murray Thomas J Abrasion resistant coated wire
US20070151743A1 (en) * 2006-01-03 2007-07-05 Murray Thomas J Abrasion resistant coated wire
DE102006037774A1 (de) * 2006-08-11 2008-02-14 Polysius Ag Walzen- oder Rollenmühle
US20140234549A1 (en) * 2013-02-15 2014-08-21 Mahle International Gmbh Thermally sprayed wear-resistant piston ring coating
JP2015063738A (ja) * 2013-09-25 2015-04-09 日本鋳鉄管株式会社 アーク溶射方法および装置
CN105970141A (zh) * 2016-07-29 2016-09-28 佛山科学技术学院 一种氮化铝喷涂装置及其喷涂方法
CN110105674B (zh) * 2019-03-25 2021-07-16 盐城华亚石油机械制造有限公司 一种高性能防腐蚀专用封隔器加工工艺
CN109778100B (zh) * 2019-04-01 2020-11-06 西安建筑科技大学 一种延寿节能形稳PbO2阳极中间层的电弧热喷涂制备方法
CN115679239B (zh) * 2022-11-07 2023-10-20 江苏迪丞光电材料有限公司 一种用于金属靶材加工生产的喷涂装置

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Also Published As

Publication number Publication date
ZA91888B (en) 1992-10-28
MX170472B (es) 1993-08-24
EP0445538A1 (en) 1991-09-11
US5066513A (en) 1991-11-19
CA2034981A1 (en) 1991-08-07
KR930007147B1 (ko) 1993-07-30
DE69108963T2 (de) 1995-08-24
CN1019642B (zh) 1992-12-30
JPH04218657A (ja) 1992-08-10
DE69108963D1 (de) 1995-05-24
ES2073598T3 (es) 1995-08-16
KR910015716A (ko) 1991-09-30
BR9100458A (pt) 1991-10-22
JP2567304B2 (ja) 1996-12-25
CN1055308A (zh) 1991-10-16

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